WO2016152547A1

WO2016152547A1 - Hydrophobic group-containing copolymer

Info

Publication number: WO2016152547A1
Application number: PCT/JP2016/057510
Authority: WO
Inventors: 大祐道尭; 光高橋
Original assignee: 株式会社日本触媒
Priority date: 2015-03-25
Filing date: 2016-03-10
Publication date: 2016-09-29
Also published as: JP6193504B2; JPWO2016152547A1; EP3275907B1; JP6659631B2; EP3275907A1; US20180118886A1; US10738156B2; EP3275907A4; JP2018039985A

Abstract

The purpose of the present invention is to provide a polymer which is capable of exerting good dispersibility with respect to hydrophobic particles. The present invention is a hydrophobic group-containing copolymer which has a structural unit (A) derived from a hydrophobic group-containing monomer represented by formula (1) and a structural unit (B) derived from a carboxylic acid monomer, and which is characterized in that: the ratio of the structural unit (A) in the copolymer is from 16% by mass to 50% by mass (inclusive) relative to 100% by mass of structural units derived from all monomers; and the weight average molecular weight of the copolymer is 10,000-1,000,000.

Description

Hydrophobic group-containing copolymer

The present invention relates to a hydrophobic group-containing copolymer. More specifically, the present invention relates to a hydrophobic group-containing copolymer useful for pitch control agents, pigment dispersants, detergent builders and the like.

In the papermaking process, an adhesive resin component contained in raw wood, an adhesive mixed in pulp, a synthetic resin, and the like are called “pitch”. The pitch particles are in a state of being colloidally dispersed in the pulp slurry, but the pitch particles are highly hydrophobic and therefore aggregate and enlarge in water. In the papermaking process, problems such as paper breakage and perforation that occur due to such a pitch occur. In order to eliminate such a problem, various pitch control agents and pitch suppression methods have been studied in the past.

As such a technique, for example, Patent Literature 1 discloses a pitch suppression method in a facility including a pulp manufacturing facility that manufactures pulp using water from a pulp raw material, Including a step of adding a chelating agent to a location where the pulp in the pulp manufacturing facility or its intermediate and water are in contact with each other so that the molar ratio of the chelating agent to calcium (chelating agent / calcium) is 1/5 or less. The chelating agent contains ethylenediamine tetraacetic acid and its salt, diethylenetriamine pentaacetic acid and its salt, triethylenetetraamine 6 acetic acid and its salt, and glycol ether diamine tetraacetic acid and its salt, or a pitch thereof. A suppression method is disclosed.

Patent Document 2 contains, as an active ingredient, a polymer comprising a constituent unit derived from a specific (meth) acryloyloxyalkyltrialkylammonium salt and a specific unit derived from a specific (meth) acrylic acid or a salt thereof. A pitch control agent for papermaking process is disclosed.

By the way, as a copolymer having a hydrophobic group, a copolymer of a monomer having a hydrophobic group and a carboxylic acid monomer is used as a detergent builder or the like. As such a technique, for example, Patent Document 3 discloses a structural unit (a) derived from a specific ether bond-containing monomer (A) and a structural unit (b) derived from a carboxyl group-containing monomer (B). The structural unit (a) is 1 to 50% by mass and the structural unit (b) is 50 to 99% by mass with respect to 100% by mass of structural units derived from all monomers. A group-containing copolymer is disclosed.

JP 2013-28887 A JP 2003-221798 A International Publication No. 2010/024448

As described above, various techniques for removing pitch in the papermaking process have been disclosed, but a polymer capable of dispersing hydrophobic particles such as pitch is sufficient in terms of dispersibility. However, there was room to develop further polymers.

This invention is made | formed in view of the said present condition, and aims at providing the polymer which can exhibit favorable dispersibility with respect to hydrophobic particle | grains.

The present inventor has made various studies on polymers that can exhibit good dispersibility with respect to hydrophobic particles. As a result, a structural unit derived from a carboxylic acid monomer and a structure derived from a hydrophobic group-containing monomer. We have found that a copolymer having a specific proportion of units and a specific weight average molecular weight exhibits excellent dispersion performance with respect to hydrophobic particles, and that the above problems can be solved brilliantly, The present invention has been achieved.

That is, the present invention provides the following formula (1);

(In the formula, R ⁰ represents a hydrogen atom or a CH ₃ group. R ^a represents ^a CH ₂ group, a CH ₂ CH ₂ group or a direct bond. R ^b represents a CH ₂ group, a CH ₂ CH ₂ group or X ¹ represents the number of units represented by (O—CH ₂ —CH (OH)) and is a number of 0 or 1. X ² represents (O—CH ₂ —CH _2). ) And is a number from 0 to 5. However, when R ^a and R ^b are a direct bond and X ¹ is 0, X ² is a number from 1 to 5. R ¹ represents a hydrophobic organic group having 1 to 20 carbon atoms) and a structural unit derived from a hydrophobic group-containing monomer (A) and a structural unit derived from a carboxylic acid monomer ( B) a hydrophobic group-containing copolymer, wherein the copolymer is such that the proportion of structural units (A) in the copolymer is 100 mass units derived from all monomers. It is a hydrophobic group-containing copolymer having a copolymer weight average molecular weight of 10,000 to 1,000,000 and not less than 16% by mass and not more than 50% by mass.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

The hydrophobic group-containing copolymer of the present invention comprises a structural unit (A) derived from a hydrophobic group-containing monomer represented by the above formula (1) and a structural unit (B) derived from a carboxylic acid monomer. It is a copolymer having.
Since the hydrophobic group-containing monomer has a hydrophobic organic group having 1 to 20 carbon atoms in R ¹ of the above formula (1), the hydrophobic group-containing copolymer of the present invention has a hydrophobic mutual group. Due to the action, it can be used well with the hydrophobic particles, prevent the particles from agglomerating and disperse the hydrophobic particles. Thereby, aggregation of hydrophobic particles can be suppressed. Further, the hydrophobic group-containing copolymer has a structural unit (B) derived from a carboxylic acid monomer, whereby the water solubility of the hydrophobic group-containing copolymer of the present invention is improved. Therefore, the hydrophobic group-containing copolymer of the present invention exhibits good dispersion performance with respect to hydrophobic particles in a hydrophilic solvent such as water by having the structural unit (A) and the structural unit (B). be able to.

The proportion of the structural unit (A) in the hydrophobic group-containing copolymer of the present invention is 16% by mass or more and 50% by mass or less with respect to 100% by mass of the structural units derived from all monomers. If the proportion of the structural unit (A) is 16% by mass or more, the copolymer of the present invention is sufficiently hydrophobic, and if it is 50% by mass or less, the water solubility of the copolymer of the present invention is low. It will be enough.
The proportion of the structural unit (A) is preferably 18 to 50% by mass, more preferably 20 to 49% by mass, still more preferably 21 to 47% by mass, and still more preferably 25 to 45% by mass. More preferably, it is 28 to 42% by mass, and particularly preferably 30 to 40% by mass.

The proportion of the structural unit (B) in the hydrophobic group-containing copolymer of the present invention is not particularly limited, but is preferably 50 to 84% by mass with respect to 100% by mass of the structural units derived from all monomers. More preferably, it is 50 to 82% by mass, still more preferably 51 to 80% by mass, still more preferably 53 to 79% by mass, still more preferably 55 to 75% by mass, and particularly preferably 58 to 82% by mass. It is 72% by mass, and more preferably 60 to 70% by mass. If the proportion of the structural unit (B) is within the above preferred range, the water-solubility of the copolymer of the present invention will be more sufficient.
In the present invention, when calculating the proportion of the structural unit (B) derived from the carboxylic acid monomer, it is calculated in terms of the corresponding acid. For example, when the structural unit (B) is a structural unit —CH ₂ —CH (COONa) — derived from sodium acrylate, the corresponding structural unit derived from acrylic acid —CH ₂ —CH (COOH) — Calculate the mass ratio (mass%).
Similarly, when calculating the mass ratio (mass%) of the carboxylic acid monomer in the monomer component, it is calculated in terms of the corresponding acid. For example, if it is sodium acrylate, a mass ratio (mass%) is calculated as acrylic acid which is a corresponding acid.

The weight average molecular weight of the hydrophobic group-containing copolymer of the present invention is 10,000 to 1,000,000.
When the weight average molecular weight is 10,000 or more, the dispersion performance of the hydrophobic group-containing copolymer can be sufficiently exhibited. The reason for this is considered to be that when the weight average molecular weight of the copolymer is 10,000 or more, microphase separation occurs and the hydrophobicity of the copolymer becomes partially larger.
The weight average molecular weight is preferably 10,000 to 500,000, more preferably 10,000 to 100,000, and still more preferably 10,000 to 50,000.
When the weight average molecular weight is in the above preferred range, the viscosity of the copolymer can be made a more suitable range, and the handling becomes excellent. Usually, the larger the weight average molecular weight of the copolymer, the better the dispersion performance, but the weight ratio of the structural unit (A) in the hydrophobic group-containing copolymer is within the above preferred range. Even when the average molecular weight is reduced, sufficient dispersion performance can be exhibited. Therefore, by combining the proportion of the structural unit (A) in the hydrophobic group-containing copolymer within the above preferable range and the weight average molecular weight within the above preferable range, the hydrophobic group-containing copolymer of the present invention is combined. The polymer is excellent in handling and can exhibit more sufficient dispersion performance, and a hydrophobic group-containing copolymer having such a combination of the proportion of the structural unit (A) and the weight average molecular weight is: 1 is one of the preferred embodiments of the present invention.
In addition, in this specification, a weight average molecular weight is a measured value by GPC (gel permeation chromatography), and can be measured on the measurement conditions mentioned later.

The carboxyl group in the hydrophobic group-containing copolymer of the present invention may be acid type or salt type, but with respect to 100 mol% of all the carboxyl groups of the hydrophobic group-containing copolymer, It is preferable that 30 to 90 mol% of the carboxyl group is in a salt form. The proportion of the salt-type carboxyl group is more preferably 40 to 80 mol%, and still more preferably 50 to 70 mol%. In the production method described later, by performing a neutralization step during or after the polymerization reaction, or by using a carboxylic acid monomer in which a part of the carboxyl group is a salt type as a raw material, The ratio of groups can be within the above preferred range.

(Hydrophobic group-containing monomer)
The hydrophobic group-containing copolymer of the present invention has a structural unit (A) derived from the hydrophobic group-containing monomer represented by the above formula (1). Since the hydrophobic group-containing monomer (hereinafter also referred to as monomer (a)) has a hydrophobic organic group having 1 to 20 carbon atoms in R ¹ of the above formula (1), The interaction allows good compatibility with the hydrophobic particles, prevents aggregation of the particles, and allows the hydrophobic particles to be dispersed.

Although it does not restrict | limit especially as said hydrophobic organic group, For example, a hydrocarbon group etc. are mentioned.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and an aryl group. As said hydrocarbon group, an alkyl group, an alkenyl group, and an aryl group are preferable, More preferably, they are an alkyl group and an alkenyl group, More preferably, it is an alkyl group.
Further, the number of carbon atoms of the hydrophobic organic group is preferably 2 to 18, more preferably 3 to 12, and still more preferably 4 to 6. If the number of carbon atoms is 4 or more, the hydrophobicity can be more fully exhibited, and if it is 6 or less, the polymerizability can be sufficiently improved.
The hydrophobic organic group may contain a hetero atom as long as it is hydrophobic. For example, the hydrophobic organic group may be a hydrocarbon group in which a hydrogen atom is substituted with a halogen or the like.

X ² in the above formula (1) represents the number of units represented by (O—CH ₂ —CH ₂ ), and is a number from 0 to 5. When X ² is 1 to 5, the hydrophobic group-containing monomer can further improve the hydrophilicity, and thus has a characteristic that it is easily copolymerized even when a hydrophilic solvent such as water is used.
X ² is preferably 1 to 3.
Also, if X ² is 0, it is possible to more sufficiently exhibit the effect of the hydrophobic group represented by R ^1. From the viewpoint of the hydrophobicity of the copolymer, X ² is more preferably 0.
Since the hydrophobic group-containing copolymer of the present invention has a good balance between hydrophilicity and hydrophobicity, it can exhibit a sufficient dispersion performance with respect to hydrophobic particles in a hydrophilic solvent. It is preferable to adjust the value of X ² according to the proportion of the structural unit (B) in the copolymer.

R ⁰ in the above formula (1) is a hydrogen atom or a CH ₃ group, preferably a hydrogen atom.
R ^a in the above formula (1) is a CH ₂ group, a CH ₂ CH ₂ group or a direct bond, preferably a CH ₂ group.
R ^b in the above formula (1) is a CH ₂ group, a CH ₂ CH ₂ group or a direct bond, preferably a CH ₂ group.
However, when R ^a and R ^b are a direct bond and X ¹ is 0, X ² is a number of 1 to 5.

X ¹ in the above formula (1) represents the number of units represented by (O—CH ₂ —CH (OH)), and is 0 or 1. X ¹ is preferably 1, and in this case, since the hydrophobic group-containing monomer has a hydroxyl group, the water solubility of the hydrophobic group-containing monomer is improved and the polymerizability is further improved. To do. If the hydrophobic group-containing monomer has such a structure, even when the proportion of the hydrophobic group-containing monomer is increased in the monomer component, the polymerization reaction can be performed more fully. it can. The structure represented by (O—CH ₂ —CH (OH)) is formed, for example, by reacting a glycidyl group with a hydroxyl group such as an adduct of alcohol or alkylene oxide.

Examples of the hydrophobic group-containing monomer include compounds obtained by reacting an alcohol having an unsaturated double bond such as vinyl alcohol, allyl alcohol and isoprenol with an alkyl glycidyl ether having 4 to 6 carbon atoms; Compound in which ethylene oxide adduct of alcohol having a heavy bond is reacted with alkyl halide having 4 to 6 carbon atoms; Allyl glycidyl ether is reacted with alcohol having 4 to 6 carbon atoms or ethylene oxide adduct of alcohol having 4 to 6 carbon atoms And the like.
As said carbon number, it is as the carbon number in the above-mentioned hydrophobic organic group.

As said hydrophobic group containing monomer, following formula (2);

(In the formula, R ⁰ represents a hydrogen atom or a CH ₃ group. R ^a represents ^a CH ₂ group, a CH ₂ CH ₂ group or a direct bond. R ¹ is a hydrophobic organic group having 1 to 20 carbon atoms. The compound represented by this is preferable.
As the ^{R 0,} is preferably a hydrogen atom, the ^{R a,} is preferably a CH ₂ group.
Specific examples and preferred examples of the hydrophobic organic group in the formula (2) are as described above.

(Carboxylic acid monomer)
The hydrophobic group-containing copolymer of the present invention has a structural unit (B) derived from a carboxylic acid monomer.
The carboxylic acid monomer (hereinafter also referred to as monomer (b)) is a monomer containing an unsaturated double bond (carbon-carbon double bond) and a carboxy group and / or a carboxylate group. is there.
The hydrophobic group-containing copolymer of the present invention has good water solubility by having the structural unit (B).

Here, the term “carboxy group and / or carboxylate group is included” means that a group represented by —COOZ (Z represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group) is included in one molecule. It means having more than one. Examples of metal atoms include alkali metals such as sodium, lithium, potassium, rubidium and cesium; alkaline earth metals such as magnesium, calcium, strontium and barium; aluminum and iron. Organic amine groups include monoethanolamine groups, diethanolamine groups, triethanolamine groups and other alkanolamine groups; monoethylamine groups, diethylamine groups, triethylamine groups and other alkylamine groups; ethylenediamine groups, triethylenediamine groups and other polyamines Groups and the like. Among these, the carboxylate group is more preferably an ammonium salt, a sodium salt or a potassium salt, and still more preferably a sodium salt.

Examples of the carboxylic acid monomer include unsaturated monocarboxylic acid monomers containing an unsaturated double bond and one carboxy group (or carboxylic acid base) in one molecule, and unsaturated in one molecule. An unsaturated dicarboxylic acid monomer containing a double bond and two carboxy groups (or carboxylate groups) is preferred.

Specific examples of the unsaturated monocarboxylic acid monomer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid and derivatives thereof, And salts thereof.
Specific examples of the unsaturated dicarboxylic acid monomer include unsaturated dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, and fumaric acid, salts thereof, and anhydrides thereof. Also, half esters of these unsaturated dicarboxylic acid monomers and alcohols having 1 to 22 carbon atoms, half amides of unsaturated dicarboxylic acid monomers and amines having 1 to 22 carbon atoms, unsaturated dicarboxylic acids It may be a half ester of a system monomer and a glycol having 2 to 4 carbon atoms, a half amide of maleamic acid and a glycol having 2 to 4 carbon atoms, or the like.

Among the carboxylic acid monomers, acrylic acid, acrylate, maleic acid, and maleate are preferable. Of these, acrylic acid and acrylate are essential.

The hydrophobic group-containing copolymer of the present invention has a structural unit (E) derived from another monomer (a monomer other than the carboxylic acid monomer and the hydrophobic group-containing monomer). It may be. The said hydrophobic group containing copolymer may have only 1 type of structural units (E), and may have 2 or more types.

The other monomer (hereinafter also referred to as monomer (e)) is not particularly limited as long as it is copolymerizable with the monomers (a) and (b), and is appropriately selected depending on the desired effect. Selectable.
Specific examples of the other monomer (e) include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 3- (meth) allyloxy-2-hydroxypropane sulfonic acid, 3- ( Sulfonic acid (salt) group-containing monomers such as (meth) allyloxy-1-hydroxypropanesulfonic acid, 2- (meth) allyloxyethylenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and salts thereof; Monomer with alkylene oxide added to unsaturated alcohol such as (meth) allyl alcohol and isoprenol, and polyalkylene glycol chain-containing monomer such as (meth) acrylic acid ester of alkoxyalkylene glycol (corresponds to monomer (a) Monomers such as vinyl pyridine and vinyl imidazole are excluded. Vinyl aromatic monomers having an aromatic hydrocarbon group; dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide; Amino-containing monomers such as dialkylaminoalkyl (meth) acrylamides such as dimethylaminopropylacrylamide, diallylamine such as diallylamine, diallylamine such as diallylamine, and quaternized products thereof; N-vinylpyrrolidone, N-vinyl N-vinyl such as formamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide, N-vinyloxazolidone Amide monomers such as (meth) acrylamide, N, N-dimethylacrylamide and N-isopropylacrylamide; Hydroxyl-containing monomers such as (meth) allyl alcohol and isoprenol; Butyl (meth) acrylate, 2- (Meth) acrylic acid alkyl ester monomers such as ethylhexyl (meth) acrylate and dodecyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) (Meth) acrylic acid hydroxyalkyl monomers such as acrylate, 4-hydroxybutyl (meth) acrylate and 2-hydroxyhexyl (meth) acrylate; vinylaryl monomers such as styrene, indene and vinylaniline; isobutylene and acetic acid Vinyl etc. Is mentioned.
The quaternized product is obtained by reacting a quaternizing agent usually used for the amino group-containing monomer. Examples of the quaternizing agent include alkyl halides and dialkyl sulfuric acid.

The content of the structural unit (E) derived from the other monomer (e), which is an optional component, is the total amount of structural units derived from all monomers forming the hydrophobic group-containing copolymer (that is, The total amount of structural units (A), (B) and (E) is preferably from 0 to 40% by mass with respect to 100% by mass. The content is more preferably 0 to 20% by mass, still more preferably 0 to 10% by mass, and particularly preferably 0% by mass.
In the case where the structural unit (E) is a structural unit derived from an amino group-containing monomer, the mass ratio relative to the total amount of structural units derived from all monomers, When calculating the mass ratio with respect to the total amount of monomers, it shall be calculated as the mass ratio of the corresponding unneutralized amine. For example, when the other monomer (e) is vinylamine hydrochloride, the mass ratio (% by mass) of vinylamine which is the corresponding unneutralized amine is calculated.
In addition, when calculating the mass ratio (mass%) of a monomer containing a quaternized amino group or a structural unit derived therefrom, the mass of the counter anion is not taken into account (not including) Shall.
When the structural unit (E) is a structural unit derived from an acid group-containing monomer, the mass ratio (mass%) relative to the total amount of structural units derived from all monomers is calculated in terms of the corresponding acid. It shall be. Moreover, when calculating the mass ratio (mass%) with respect to the total amount of all the monomers of an acid group containing monomer, it shall calculate in conversion to a corresponding acid.

<Method for producing hydrophobic group-containing copolymer>
The production of the hydrophobic group-containing copolymer of the present invention is not particularly limited, and examples thereof include a method of polymerizing the monomer component.
The monomer component used in the production of the hydrophobic group-containing copolymer of the present invention includes the carboxylic acid monomer and the hydrophobic group-containing monomer as essential components, and optionally other monomers. May be included.
The carboxylic acid monomer may be an acid type or a salt type (neutralized type).
The content ratios of the carboxylic acid monomer, the hydrophobic group-containing monomer and the other monomer in the monomer component are as described above.

(Neutralization process)
When all of the carboxylic acid monomers contained in the monomer component are acid type or partly salt type, a neutralization step may be performed during the polymerization reaction and / or after the polymerization reaction.
Preferably, a neutralization step is performed after the polymerization reaction. By bringing the pH close to neutral after the reaction, corrosion or the like can be more sufficiently suppressed when the storage container is a metal.
In the neutralization step, an alkali component is preferably used.
As the alkali component, those commonly used can be used, and specific examples thereof include those described in International Publication No. 2011/158945.
The alkali component is preferably an alkali metal hydroxide, more preferably sodium hydroxide.
The usage-amount of the alkali component used at the said neutralization process can be set so that the ratio of the salt of the carboxyl group with respect to all the carboxyl groups of the said hydrophobic group containing copolymer may become the above-mentioned range.

(Polymerization initiator)
The carboxylic acid-based water-soluble polymer of the present invention is preferably obtained by polymerizing a monomer component in the presence of a polymerization initiator (hereinafter also referred to as an initiator).
As said polymerization initiator, what is normally used as a polymerization initiator can be used, For example, persulfate; Hydrogen peroxide; Azo compound; Organic peroxide etc. are suitable. Specific examples thereof are the same as those described in International Publication No. 2010/024448. These polymerization initiators may be used alone or in the form of a mixture of two or more. Since the molecular weight distribution of the polymer tends to be small, it is preferable to use only one kind. The polymerization initiator is preferably a persulfate, and more preferably sodium persulfate.
The amount of the polymerization initiator used is not particularly limited, but is preferably 10 g or less, more preferably 1 to 5 g with respect to 1 mol of all monomer components.

(Chain transfer agent)
In the method for producing a carboxylic acid-based water-soluble polymer of the present invention, a chain transfer agent can be used in addition to the polymerization initiator. The chain transfer agent that can be used in this case is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and those that are usually used as chain transfer agents can be used. Specifically, thiol chain transfer agent; halide; secondary alcohol; phosphorous acid, phosphite, hypophosphorous acid, hypophosphite, etc .; sulfurous acid, hydrogen sulfite, dithionic acid, Metabisulfite and its salts (sodium bisulfite, potassium bisulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.), etc. Specific examples thereof are the same as those described in International Publication No. 2010/024448. The said chain transfer agent may be used independently and may be used with the form of 2 or more types of mixtures.
Among the chain transfer agents, it is preferable to use sulfite or sulfite. That is, it is preferable to use at least sulfurous acid and / or sulfite (hereinafter referred to as “sulfurous acid (salt)”) as the chain transfer agent.

The sulfurous acid (salt) refers to sulfurous acid or hydrogen sulfite, or a salt thereof, and a form in which sulfurous acid / bisulfite is a salt is preferable. When sulfite / bisulfite is a salt, in addition to the examples described above, salts of metal atoms, ammonium or organic ammonium are preferred. Examples of the metal atom include monovalent metal atoms of alkali metals such as lithium, sodium and potassium; divalent metal atoms of alkaline earth metals such as calcium and magnesium; trivalent metal atoms such as aluminum and iron And the like are preferred. As the organic ammonium (organic amine), alkanolamines such as ethanolamine, diethanolamine, and triethanolamine, and triethylamine are preferable. Further, it may be ammonium. Therefore, examples of the sulfite preferably used in the present invention include sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium sulfite, potassium sulfite, ammonium sulfite and the like, and sodium bisulfite is particularly suitable.
In addition, the said sulfurous acid (salt) may be used independently and may be used with the form of 2 or more types of mixtures.

The amount of the chain transfer agent added is not particularly limited, but is preferably 1 to 20 g with respect to 1 mol of all monomer components. More preferably, it is 2 to 15 g. If it is less than 1 g, the molecular weight may not be controlled. Conversely, if it exceeds 20 g, the chain transfer agent may remain or the pure polymer content may decrease.

(Decomposition catalyst, reducing compound)
In the method for producing the hydrophobic group-containing copolymer of the present invention, a polymerization initiator decomposition catalyst or a reducing compound (also referred to as a reaction accelerator) is used (added to the polymerization system) in addition to the polymerization initiator. Also good.
Examples of the compound that acts as a decomposition catalyst or reducing compound for the polymerization initiator include heavy metal ions (or heavy metal salts). That is, the method for producing the hydrophobic group-containing copolymer of the present invention may use (add to the polymerization system) heavy metal ions (or heavy metal salts) in addition to the polymerization initiator and the like. In the present specification, the heavy metal ion means a metal having a specific gravity of 4 g / cm ³ or more.

Specific examples of the heavy metal ions include those described in International Publication No. 2010/024448. These heavy metals can be used alone or in combination of two or more. Among these, iron is more preferable.
The ionic valence of the heavy metal ions is not particularly limited. For example, when iron is used as the heavy metal, the iron ions in the initiator may be Fe ²⁺ or Fe ³⁺ , and these may be combined. May be.
When iron is used as the heavy metal ion, the mole salt (Fe (NH ₄ ) ₂ (SO ₄ ) ₂ · 6H ₂ O), ferrous sulfate · 7 hydrate, ferrous chloride, ferric chloride, etc. It is preferable to use a heavy metal salt or the like.

The content of the heavy metal ions is preferably 0.1 to 10 ppm with respect to the total mass of the polymerization reaction solution at the completion of the polymerization reaction (after neutralization when a neutralization step is performed after the polymerization reaction). . When the content of heavy metal ions is 0.1 ppm or more, the effect of heavy metal ions can be expressed more sufficiently, and when the content is 10 ppm or less, the resulting polymer can be more excellent in color tone.

In the method for producing the hydrophobic group-containing copolymer (aqueous solution) of the present invention, in addition to the polymerization initiator, the chain transfer agent, and the reaction accelerator, a pH adjuster, a buffering agent, or the like may be used as necessary. it can.

(Polymerization solution)
The hydrophobic group-containing copolymer of the present invention is preferably produced by solution polymerization. The solvent that can be used in this case is preferably a mixed solvent in which 50% by mass of water or water is used with respect to the total solvent. It is more preferable to use only water as the solvent. Here, as the organic solvent that can be used together with water at the time of polymerization, those usually used can be used, and specific examples thereof are the same as those described in International Publication No. 2010/024448. It is done.

The polymerization reaction preferably has a solid content concentration after polymerization of 10% by mass to 60% by mass with respect to 100% by mass of the polymerization solution. 15 to 50% by mass is more preferable, and 20 to 45% by mass is even more preferable.

(Other manufacturing conditions)
The temperature during the polymerization is preferably 70 ° C. or higher, more preferably 75 to 110 ° C., and still more preferably 80 to 105 ° C.
The pressure in the reaction system in the polymerization reaction may be normal pressure (atmospheric pressure), reduced pressure, or increased pressure.
The atmosphere in the reaction system may be an air atmosphere or an inert atmosphere, and is not particularly limited. Economically, it is preferably performed in an air atmosphere.

The production method of the present invention may be provided with an aging step for the purpose of increasing the polymerization rate of the monomer after the addition of all the raw materials used is completed. The aging time is usually 1 to 120 minutes, preferably 10 to 100 minutes, more preferably 30 to 60 minutes. When the aging time is less than 1 minute, the monomer component may remain due to insufficient aging, and impurities due to the residual monomer are formed and the performance tends to be lowered.
The preferable temperature of the polymer solution in the aging step is in the same range as the polymerization temperature.

<Use of hydrophobic group-containing copolymer>
As the hydrophobic group-containing copolymer (or a polymer composition containing the same) of the present invention, it is excellent in the dispersion performance of hydrophobic particles, so that it can be suitably used for, for example, a pitch control agent and a pigment dispersant. Moreover, it can be used suitably also for uses, such as a detergent builder or a detergent composition.
Below, the use of a pitch control agent, a pigment dispersant, and a detergent builder / detergent composition is taken as an example, and the case where the hydrophobic group-containing copolymer of the present invention is used for these uses will be described.

<Pitch control agent>
This invention is also a pitch control agent containing the hydrophobic group containing copolymer of this invention.
The content of the hydrophobic group-containing copolymer in the pitch control agent is not particularly limited, but is preferably 20 to 100% by mass, more preferably 50 to 100% by mass with respect to 100% by mass of the pitch control agent. It is.

The pitch control agent may contain other additives in addition to the hydrophobic group-containing copolymer. Other additives are not particularly limited, and examples include chelating agents, surfactants, and conventional pitch control agents.

Although it does not restrict | limit especially as said chelating agent, For example, Aminocarboxylic acid (salt), such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and these salts; Phosphonic acids, such as hydroxy ethylidene diphosphonic acid; Examples thereof include carboxylic acids (salts) such as acid, succinic acid, oxalic acid, phthalic acid, malic acid, tartaric acid and salts thereof.

Although it does not restrict | limit especially as said surfactant, For example, nonionic surfactants, such as polyoxyethylene alkyl ether, etc. are mentioned.
Although it does not restrict | limit especially as said conventional pitch control agent, For example, a talc, a cationic polymer, a solvent, an enzyme, etc. are mentioned.

The content of other additives in the pitch control agent is not particularly limited, but is preferably 0 to 80% by mass, more preferably 0 to 50% by mass with respect to 100% by mass of the pitch control agent.

<Pigment dispersant>
The present invention is also a pigment dispersant containing the hydrophobic group-containing copolymer of the present invention.
The content of the hydrophobic group-containing copolymer in the pigment dispersant is not particularly limited, but is preferably 20 to 100% by mass, more preferably 50 to 100% by mass with respect to 100% by mass of the pigment dispersant. It is.

The pigment dispersant may contain other additives in addition to the hydrophobic group-containing copolymer. Other additives are not particularly limited, and examples thereof include condensed phosphoric acid and salts thereof, phosphonic acid and salts thereof, and polyvinyl alcohol.

The content of other additives in the pigment dispersant is not particularly limited, but is preferably 0 to 80% by mass, more preferably 0 to 50% by mass with respect to 100% by mass of the pigment dispersant.

<Detergent builder / detergent composition>
The present invention is also a detergent builder or detergent composition comprising the hydrophobic group-containing copolymer of the present invention.
The content of the hydrophobic group-containing copolymer in the detergent composition is not particularly limited, but from the viewpoint that excellent builder performance can be exhibited, the content of the hydrophobic group-containing copolymer is determined by the detergent composition. Preferably, the content is 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, and still more preferably 0.5 to 5% by mass.

Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. Specific forms of these surfactants and additives are not particularly limited, and conventionally known knowledge can be appropriately referred to in the detergent field. The detergent composition may be a powder detergent composition or a liquid detergent composition.

The surfactant is one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant. When two or more kinds are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass with respect to the total amount of the surfactant. Or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.

Examples of anionic surfactants include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate , Saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate ester or Its salts are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these anionic surfactants.

Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin mono Esters, alkylamine oxides and the like are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these nonionic surfactants.

As the cationic surfactant, a quaternary ammonium salt or the like is suitable. As the amphoteric surfactant, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant, and the like are suitable. The alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may be branched from an alkyl group such as a methyl group.

The blending ratio of the surfactant is usually 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass, particularly preferably based on the total amount of the detergent composition. Is 25 to 40% by mass. If the surfactant content is too small, sufficient detergency may not be achieved, and if the surfactant content is too high, the economy may be reduced.

Additives include anti-redeposition agent to prevent redeposition of contaminants such as alkali builder, chelate builder, sodium carboxymethyl cellulose, stain inhibitor such as benzotriazole and ethylene-thiourea, soil release agent, color transfer Inhibitors, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, dyes A solvent or the like is preferable. In the case of a powder detergent composition, it is preferable to blend zeolite.

The detergent composition may contain another detergent builder in addition to the hydrophobic group-containing copolymer of the present invention. Examples of other detergent builders include, but are not limited to, alkali builders such as carbonates, hydrogen carbonates, and silicates, tripolyphosphates, pyrophosphates, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, And acid salt, copolymer salt of (meth) acrylic acid, acrylic acid-maleic acid copolymer, fumarate, chelate builder such as zeolite, and carboxyl derivative of polysaccharide such as carboxymethylcellulose. Examples of the counter salt used in the builder include alkali metals such as sodium and potassium, ammonium and amine.

The total blending ratio of the additive and other detergent builder is usually preferably 0.1 to 50% by mass with respect to 100% by mass of the cleaning composition. More preferably, it is 0.2 to 40% by mass, still more preferably 0.3 to 35% by mass, particularly preferably 0.4 to 30% by mass, and most preferably 0.5 to 20% by mass. is there. If the additive / other detergent builder content is less than 0.1% by mass, sufficient detergent performance may not be achieved, and if it exceeds 50% by mass, the economy may be reduced.

In addition, the concept of the above-mentioned detergent composition includes specific detergents such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance one of the components. Also included are detergents that are only used.

When the detergent composition is a liquid detergent composition, the amount of water contained in the liquid detergent composition is usually preferably 0.1 to 75% by mass, more preferably based on the total amount of the liquid detergent composition. Is 0.2 to 70% by mass, more preferably 0.5 to 65% by mass, still more preferably 0.7 to 60% by mass, particularly preferably 1 to 55% by mass, The amount is preferably 1.5 to 50% by mass.

Proteases, lipases, cellulases, and the like are suitable as enzymes that can be incorporated into the cleaning composition. Of these, proteases, alkaline lipases, and alkaline cellulases that are highly active in an alkaline cleaning solution are preferred.

The amount of the enzyme added is preferably 5% by mass or less with respect to 100% by mass of the cleaning composition. If it exceeds 5% by mass, improvement in detergency cannot be seen, and the economy may be reduced.

Even when the detergent composition is used in an area of hard water (for example, 100 mg / L or more) having a high concentration of calcium ions and magnesium ions, salt precipitation is small and has an excellent cleaning effect. This effect is particularly pronounced when the detergent composition contains an anionic surfactant such as LAS.

The hydrophobic group-containing copolymer of the present invention has the above-described configuration and is excellent in dispersibility of hydrophobic particles, and therefore can be suitably used for pitch control agents, pigment dispersants, detergent builders / detergent compositions, and the like. . Moreover, it can use suitably also for uses, such as a water treatment agent, a scale inhibitor, the scale inhibitor for RO membranes, and the scale inhibitor for oil fields.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

<Measurement conditions of weight average molecular weight>
Equipment: High speed GPC equipment manufactured by Tosoh Corporation (HLC-8320GPC)
Detector: RI
Column: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B manufactured by Showa Denko KK
Column temperature: 40 ° C
Flow rate: 0.5 ml / min
Calibration curve: POLYACRYLIC ACID STANDARD made by Soka Science Co., Ltd.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio)

<Example 1>
(Monomer synthesis)
A 500 mL glass four-necked flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 370.0 g of n-butyl alcohol and 4.27 g of sodium hydroxide in pellet form and stirred to 60 ° C. The temperature rose. Next, 57.0 g of allyl glycidyl ether (hereinafter also referred to as “AGE”) was added over 30 minutes, and then reacted for 5 hours. This solution was transferred to a 1,000 ml eggplant flask and desolvated with a rotary evaporator. To this, 200.0 g of a 20% by mass aqueous sodium chloride solution was added, this aqueous solution was transferred to a 500 ml separatory funnel, shaken well, and then allowed to stand until the layers were separated, and the lower layer was removed. The remaining upper layer was transferred to a 300 ml eggplant flask and desolvated with a rotary evaporator. The precipitated salt was removed by filtration to obtain monomer (1).

(polymerization)
A 1,000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 100.0 g of pure water and 0.0116 g of Mole salt, and the temperature was raised to 85 ° C. while stirring to polymerize the reaction. It was a system. Next, 175.0 g of an 80% aqueous acrylic acid solution (hereinafter also referred to as “80% AA”), 60.0 g of monomer (1), 15 in a polymerization reaction system maintained at 85 ° C. with stirring. 49.8 g of an aqueous solution of sodium persulfate (hereinafter also referred to as “15% NaPS”) and 19.4 g of an aqueous solution of 35% sodium bisulfite (hereinafter also referred to as “35% SBS”) More dripped. The dropping time of each solution was 180 minutes for 80% AA, 120 minutes for monomer (1), 210 minutes for 15% NaPS, and 175 minutes for 35% SBS. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, 137.8 g of a 48% aqueous sodium hydroxide solution (hereinafter also referred to as “48% NaOH”) was gradually added dropwise while stirring and allowing the polymerization reaction liquid to cool, thereby neutralizing the polymerization reaction liquid. In this way, a polymer aqueous solution having a solid content concentration of 46% was obtained. The weight average molecular weight of the polymer was 55,000.

<Example 2>
A 1,000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 100.0 g of pure water and 0.0126 g of Mole salt, and the temperature was raised to 85 ° C. while stirring to polymerize the reaction. It was a system. Next, 159.4 g of 80% AA, 85.0 g of monomer (1), 88.9 g of 15% NaPS, and 38% of 35% SBS were placed in a polymerization reaction system maintained at 85 ° C. with stirring. 0.1 g was added dropwise in the same manner as in Example 1. After completion of the dropwise addition, the reaction solution was kept at 85 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, 125.4 g of 48% NaOH was gradually added dropwise while stirring and allowing the polymerization reaction liquid to cool, thereby neutralizing the polymerization reaction liquid. In this way, a polymer aqueous solution having a solid content concentration of 46% was obtained. The weight average molecular weight of the polymer was 18,000.

<Comparative Example 1>
A 45% aqueous solution of sodium polyacrylate having a weight average molecular weight of 50,000 (manufactured by Nippon Shokubai Co., Ltd.) was used as a comparative polymer (1).

<Comparative example 2>
A glass separable flask with a capacity of 1,000 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 146.8 g of pure water and 0.0186 g of Mole salt, and heated to 85 ° C. while stirring. A polymerization reaction system was used. Next, in a polymerization reaction system maintained at 85 ° C. with stirring, 270.0 g of 80% AA, 11 g of monomer (1), 60 g of 15% NaPS, and 20 g of 35% SBS were respectively provided in separate nozzles. More dripped. The dropping time of each solution was 180 minutes for 80% AA, 140 minutes for monomer (1), 190 minutes for 15% NaPS, and 175 minutes for 35% SBS. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After the completion of the dropwise addition of 80% AA, the reaction solution was kept at 85 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, 197.5 g of 48% NaOH was gradually added dropwise while stirring and allowing the polymerization reaction liquid to cool, thereby neutralizing the polymerization reaction liquid. Thus, a polymer aqueous solution having a solid content concentration of 45% was obtained. The weight average molecular weight of the polymer was 35,000.

<Comparative Example 3>
A glass separable flask with a capacity of 1,000 mL equipped with a reflux condenser and a stirrer (paddle blade) was charged with 146.8 g of pure water and 0.0186 g of Mole salt, and heated to 85 ° C. while stirring. A polymerization reaction system was used. Next, 270.0 g of 80% AA, 24 g of monomer (1), 80 g of 15% NaPS, and 30 g of 35% SBS were separately added to a separate nozzle in a polymerization reaction system maintained at 85 ° C. with stirring. More dripped. The dropping time of each solution was 180 minutes for 80% AA, 140 minutes for monomer (1), 190 minutes for 15% NaPS, and 175 minutes for 35% SBS. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After the completion of the dropwise addition of 80% AA, the reaction solution was kept at 85 ° C. (ripening) for another 30 minutes to complete the polymerization. After completion of the polymerization, 197.5 g of 48% NaOH was gradually added dropwise while stirring and allowing the polymerization reaction liquid to cool, thereby neutralizing the polymerization reaction liquid. Thus, a polymer aqueous solution having a solid content concentration of 45% was obtained. The weight average molecular weight of the polymer was 60,000.

<Measurement of carbon black dispersibility>
The polymers obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were measured for carbon black dispersibility by the following method.
In measuring the carbon black dispersibility, first, a buffer solution and a 0.1% polymer aqueous solution were prepared. The above buffer solution was prepared by adding pure water to 6.76 g of glycine, 5.26 g of sodium chloride and 0.50 g of 48% sodium hydroxide to make the total amount 60.0 g, and then 0.123 g of calcium chloride dihydrate, Magnesium chloride hexahydrate 0.056 g was added, and pure water was added to make 1000.0 g. The 0.1% aqueous polymer solution used was prepared by diluting the polymer obtained in Examples 1-2 or Comparative Examples 1-3 with an appropriate amount of water to a solid content concentration of 0.1% by mass. .
Next, each solution and carbon black powder were charged into a 30 ml test tube in a predetermined order and in a predetermined amount. The predetermined order and the predetermined amount are as follows: 0.03 g of carbon black powder is charged as the first, 27.0 g of buffer solution is charged as the second, and finally 0.1% polymer aqueous solution 3 is charged. 0.0 g was charged.
After each solution and carbon black powder were charged in this order, the test tube was capped and slowly reversed up and down 60 times to stir the contents. Thereafter, the mixture was allowed to stand at room temperature for 20 hours. After 20 hours, the supernatant was immediately put into a 1 cm quartz cell, and the absorbance at a UV wavelength of 380 nm was measured with a spectrophotometer (measurement apparatus; UV-1800 manufactured by Shimadzu Corporation). did. The results are shown in Table 1. A higher absorbance indicates that the carbon black powder is well dispersed.

Claims

Following formula (1);

(In the formula, R 0 represents a hydrogen atom or a CH 3 group. R a represents a CH 2 group, a CH 2 CH 2 group or a direct bond. R b represents a CH 2 group, a CH 2 CH 2 group or X 1 represents the number of units represented by (O—CH 2 —CH (OH)) and is a number of 0 or 1. X 2 represents (O—CH 2 —CH 2). ) And is a number from 0 to 5. However, when R a and R b are a direct bond and X 1 is 0, X 2 is a number from 1 to 5. R 1 represents a hydrophobic organic group having 1 to 20 carbon atoms) and a structural unit derived from a hydrophobic group-containing monomer (A) and a structural unit derived from a carboxylic acid monomer ( B) a hydrophobic group-containing copolymer comprising:
In the copolymer, the proportion of the structural unit (A) in the copolymer is 16% by mass or more and 50% by mass or less with respect to 100% by mass of the structural units derived from all monomers,
A hydrophobic group-containing copolymer, wherein the copolymer has a weight average molecular weight of 10,000 to 1,000,000.
The hydrophobic group-containing monomer is represented by the following formula (2);

(In the formula, R 0 represents a hydrogen atom or a CH 3 group. R a represents a CH 2 group, a CH 2 CH 2 group or a direct bond. R 1 is a hydrophobic organic group having 1 to 20 carbon atoms. The hydrophobic group-containing copolymer according to claim 1, which is a compound represented by the formula:
A pitch control agent comprising the hydrophobic group-containing copolymer according to claim 1.
A pigment dispersant comprising the hydrophobic group-containing copolymer according to claim 1.